CS237335B2 - Fungicide agent and agent for regulation of growth of plants and processing of active components - Google Patents

Abstract

Compounds which are ether derivatives of substituted 1-hydroxyalkyl-azoles, of the general formula <IMAGE> (I) in which A represents a nitrogen atom or a CH group, B represents oxygen, sulphur or a CH2 group, R1 represents a substituted alkyl, optionally substituted cycloalkyl or optionally substituted phenyl radical or, if either A represents a nitrogen atom, or if A represents the CH group and at the same B represents oxygen or sulphur, R1 also represents an unsubstituted alkyl radical, R2 represents an alkyl, alkenyl, alkinyl, optionally substituted phenyl or optionally substituted benzyl radical, Z represents a halogen atom or an alkyl, cycloalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally substituted phenylalkoxy radical and m is 0, 1, 2 or 3, and acid addition salts and metal salt complexes thereof, are novel, are prepared as described, and find use as fungicides and as agents for regulating plant growth.

Description

The present invention relates to a fungicidal composition and a plant growth control composition which contain novel ether derivatives of substituted 1-hydroxyalkylazoles as active ingredients. The invention further relates to a process for the preparation of these novel compounds and to their use as fungicides and plant growth regulators.

It is already known that certain biphenylylhydroxyalkylazole derivatives such as 2- (4-biphenylyl) -1- (2,4-dichlorophenyl) - or -phenyl-3- (1,2,4-triazol-1-yl) ) -2-propanol and 4-blphenylyl-2-chloro or -fluorophenyl- (1,2,4-triazr-1-ylmethyl) carbinol, have good fungicidal properties and also have the ability to control plant growth in certain amounts applied ( cf. DE-OS 29 20 374).

However, the efficacy of these compounds is not always entirely sufficient, especially at low application rates and low concentrations.

Furthermore, ether derivatives of certain hydroxyalkylimidazrels are known from the patent literature (cf. U.S. Patent Nos. 4,123,542 and 4,277,475) which have an effect against pathogenic fungi occurring in human medicine and can also be used as medicaments and can also be used as contraceptives (U.S. Pat. No. 4,277,475).

It is further known that certain phenyltriazolylethanol derivatives, such as 1- (4-chlorophenyl) -2- (1,2,4-riazooll-yl) -1-ethanol, have fungicidal properties (cf. DE -OS 24'31 407). However, the effect of these - compounds - is also not always sufficient, especially at low application rates and concentrations.

We have now found novel ether derivatives of substituted 1-hydroxyalkylazoles of formula (I)

in which

B is oxygen or CH2,

R1 is C1-C4alkyl,

R ² represents an alkyl group having 1 to 4 carbon atoms,

Z is halogen or a (C 1 -C 4) alkyl group and m is 1 or 2, as well as their acid addition salts. .....

The compounds of formula I have one asymmetric carbon atom and can therefore be formed in both optical isomeric forms.

The present invention provides a fungicidal and plant growth regulating composition, characterized in that it comprises at least one substituted 1-hydroxyalkylazole ether derivative of the formula I or an acid addition salt thereof as an active ingredient.

According to the invention, novel ether derivatives of substituted 1-hydroxyalkylazoles of formula I are prepared by reacting alkoxides of 1-hydroxyalkylazoles of formula II

OM

and others have considerable ability to control plant growth.

Surprisingly, the ether derivatives of the formula I according to the invention exhibit better fungicidal activity and have a better ability to control the growth of plants than the aforementioned triazolyl derivatives which are known in the art. The active compounds according to the invention thus represent an enrichment of the technique.

The ether derivatives of the substituted 1-hydroxyalkylazoles according to the invention are generally defined by formula I. Preferred are those compounds of formula I in which:

R ¹ represents a straight or branched alkyl group of · 1-4 carbon atoms;

B, R 2, Z and m have the above-mentioned preferred meanings.

Particularly preferred are furthermore those compounds of the formula I in which:

R-1 represents tert-butyl, isopropyl or methyl, and

B, R 2, Z and m are as defined above.

Particularly preferred are further those compounds of the general formula I in which

R1 is tert-butyl, isopropyl or methyl;

B means · oxygen and .........

R2, Z and m have the above meanings.

Preferred compounds of the invention are also acid addition products and those ether derivatives of substituted 1-hydroxyalkylazoles of the general formula I, in which the substituents B, R 1, R 2 and have the meanings already indicated as being preferred for these substituents.

Acids which may be added preferably include hydrohalic acids such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, monobasic and dibasic carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

If, for example, 2- (4-chlorophenoxymethyl) -3,3-dimethyl-4- (1,2,4-thiazol-1-yl) butan-2-ol and iodomethane are used as starting materials, the reaction can be carried out according to the invention. of the invention shown by the following reaction scheme:

(II) in which:

B, R1, Z and m have the meanings given above and

M represents an alkali metal, a quaternary ammonium group or a phosphonium group, with a halide of the general formula ΪΙΙ

R ² - Hal (III) in which

R2 is as defined above and

Hal is halogen, in the presence of a diluent at a temperature between 0 and 120 ° C, and optionally an acid is added to the compound of formula I thus obtained.

The novel ether derivatives of the substituted Thydroxyalkylazoles of formula I have been found to have potent fungicidal properties237335

The alkoxides of the 1-hydroxyalkylazoles used as starting materials in the process of the invention are generally defined by Formula II. In this formula, the general symbols B, R ¹ , Z and the index m preferably mean those values already mentioned in connection with the description of the compounds of the formula I according to the invention as being preferred for these substituents or for this index m. lithium, sodium and potassium. M is preferably in addition the following quaternary ammonium groups: tetrabutylammonium, N-benzyl-N, N, N-trimethylammonium, hexadecyltrimethylammonium, tetraethylammonium, tetramethylammonium, methyltrioctylammonium, N-phenyl-N, N, N-trimethylammonium , N- (4-methylbenzyl) -Ν, Ν, Ν-trimethylammonium, N-benzyl-N, N-dimethyl-N-dodecylammonium, N, N-dibenzyl-N, N-dimethylammonium, benzyldimethyl-n- hexadecylammonium, benzyltributylammonium, benzyltriethylammonium, butyltripropylammonium, octadecyltrimethylammonium, tetrahexylammonium, tetraoctylammonium and hexadecylpyridinium; as well as preferably the following phosphonium groups: tetrafenylphosphonium group, hexadecyltributylphosphonium group, ethyltriphenylphosphonium group or methyltriphenylphosphonium group.

The alkoxides of the formula II are not yet known. However, they can be obtained in a manner known per se by reacting the corresponding substituted 1-hydroxyalkylazoles of the general formula IV

(IV) in which:

B, R ¹ , Z, and m are as defined above, reacted with suitable strong bases such as alkali metal amides or alkali metal hydrides, quaternary ammonium hydroxides or phosphonium hydroixides in an inert solvent such as dioxane at room temperature.

The substituted 1-hydroxyalkylazoles of the general formula IV are partly known compounds (cf. DE-OS 30 18 866) and are partially described in U.S. Pat. These compounds are obtained by treating the oxiranes of the general formula V

(IN)

B, R ¹ , Z and m are as defined above, with triazole of formula VI wherein (VI) in the presence of an inert organic solvent such as ethanol and optionally in the presence of a base such as sodium ethoxide optionally at 0 1 to 2.4 MPa, at temperatures between 60 and 150 ° C, or by the formation of azolylmethyloxiranes of formula VII

And i

CH -e - R ¹

I ^CH 2 s in m-and (VII) in which

R 1 is as defined above, acting on phenols of formula VIII

(VIII) in which:

Z and m are as defined above

Bi is oxygen, in the presence of an inert organic solvent, such as ethanol, and optionally in the presence of a base, such as sodium ethoxide, optionally at a pressure of 1 to 50 bar, at temperatures between 60 and 100 ° C.

The oxiranes of the formula V are partly known compounds (cf. DE-OS 30 18 866), partly described in U.S. Pat. čs. No. 236,870. These compounds were obtained by ketones of the general formula IX &apos;

B, R, Z and m are as defined above, reacted either

a) with dimethylxxosuffonium mercury (X)

8+ δ ^- (CH 3) 2 SOCH 2. (X) in a manner known per se in the presence of a diluent, such as dimethyl sulfoxide, at temperatures between 20 and 80 ° C [cf. here also the data in J. Am. Chem. Soc. 87, 1363-1364 (1965)], or (3) with trimethylsulfonylmethyl sulfate. XI ω of [CH _{3) 3]} CH ₃ SO ₄ (XI) in a known manner · in the presence of an inert organic solvent such as acetonitrile in the presence of a base such as sodium methoxide at a temperature between 0 and 60 ° C, preferably at room temperature [cf. also data in Heterocycles 8, 397, (1977)].

The oxiranes V thus obtained can be used directly for the next reaction without isolation.

The ketones of the formula IX which are required for the preparation of oxiranes of the formula V as starting materials are known (cf., for example, German Patent Specification No. 22 01 063, DE-OS 26 32 603, DE-OS 26 32 602, DE-OS 26 35 664). , DE-OS 26 35 666, DE-OS 27 05 678, DE-OS 29 18 894, DE-OS 29 18 893, German Patent No. 22 01 063, DE-OS 27 05 678, DE-OS 27 37 489), optionally described in DE-OS 30 21 551, DE-OS 31 19 390, DE-OS 3101143, or can be prepared in principle by known methods.

The dimethyloxosulfonismmethylide of formula X, which is required as starting material in process variant a), is also a known compound [cf. J. Am. Chem. Soc. 87, 1363-1364 (1965)]. In the above reaction, it is processed in a freshly prepared state by producing in situ by reacting trimethylsulfoxosulfonium iodides with sodium hydride or sodium amide in the presence of a diluent.

The trimethylsulfonism methyl sulfate of formula XI, which is needed as a starting material in process variant β), is also a known compound [cf. Heterocycles 8, 397 (1977)]. This material is also used in the freshly prepared state in the above reaction by being prepared by reacting dimethylsulfide with dimethylsulfate in situ.

(IX) wherein

The azolylmethyloxiranes of the formula VII which are used as further starting materials in the preparation of the 1-hydroxyalkylazoles of the formula IV are not yet known. These substances are, however, partly described in DE-OS 31 11 238, or can be obtained in a generally known manner by azoloketony formula XII ^W ^ \ _Ί (XII) in which

R ¹ has the above meaning, epoxidized corresponding manner as described above рго process variant a) and / 3).

The azoloketones of the formula (XII) are known compounds (cf. DE-OS 24 31 407, DE-OS 26 38 470, DE-OS 28 20 361 and DE-OS 30 48 266) or can be prepared in principle by known methods.

The azoles of the formula VI or the phenols of the formula VII, which are further used as starting materials for the preparation of the 1-hydroxyalkylazoles of the formula IV, are generally known compounds of organic chemistry. The halides which are further used as starting materials for the process according to the invention are generally defined by formula III. In this formula the symbol R @ ² preferably have those meanings which have already been mentioned in connection with the description of the compounds of formula I according to the invention as preferred for this substituent. Hal is preferably chlorine, bromine or iodine.

Halides of the formula III are generally known compounds of organic chemistry.

As examples of substituted 1-hydroxyalkylazoles of formula IX, which are intermediates for alkoxides of formula. II used in the process according to the invention, the following compounds of the general formula IV can be mentioned

z _m в Rl

4-Cl O C (CH ₃ hr 4-Cl CH ₂ C (CH3) ₃ 4-Cl, _2-CH3 0 C (CH ₃ hr 2,4-Cl ₂ 0 C (CH3) _{3 4-CH3} 0 C (CH ₃ hr _2-CH3 0 C (CH ₃ ) ₃ 4-F CH ₂ C (CH ₃ hr 2-C1 0 C [CH3) ₃ 2,4-Cl ₂ CH ₂ С (СН ₃ ) з 2-CH _third CH ₂ C (CH ₃ hr 4-F 0 С (С ₃ ) з 3-C1 0 С (СН ₃ ) з 2-Cl, 4-F 0 С [СН _{3] 3 3,4-Cl2} 0 С (СН _{3] 3} 4-CH3 CH ₂ С (С ₃ ) з - 0 С (СН _{3) 3} 4-C (CH3) ₃ 0 С (СН ₃ ) з 4-Cl with С (СН _{3) 3}

Suitable diluents for the reaction according to the invention are inert organic solvents. These preferably include ethers, such as diethyl ether or dioxane, aromatic hydrocarbons, such as benzene, and in each case also chlorinated hydrocarbons, such as chloroform, methylene chloride or carbon tetrachloride, and hexamethyltriophosphoric triamide.

The reaction temperatures can be varied within a wide range when carrying out the process according to the invention. In general, the reaction is carried out at temperatures between 0 and 120 ° C, preferably between 20 and 100 ° C.

In the process according to the invention, preferably 1 to 2 moles of halide (III) are used per mole of alkoxide (II). In order to isolate the reaction products, the reaction mixture was freed from the solvent and water and an organic solvent were added to the residue.

The organic phase is separated and worked up and purified in the usual manner.

Preferably, a substituted 1-hydroxyalkylazole derivative of formula (IV) is used as the starting material, which is converted to an alkali metal alkoxide of formula (II) by treatment with an alkali metal hydride or an alkali metal amide in a suitable organic solvent. is reacted immediately with a halide of the formula III, whereby the compound of the invention of the formula I is obtained in a single step by cleaving the alkali metal halide

According to a further preferred embodiment of the process according to the invention, the preparation of the alkoxides of the formula II and the reaction according to the invention are expediently carried out in a two-phase system such as, for example, an aqueous mixture. sodium or potassium hydroxide and toluene or methylene chloride, with the addition of 0.01 to 1 mol of phase transfer catalyst. such as ammonium compounds or phosphonium compounds, in which the alkoxides react with the halides found in the organic phase in the organic phase or at the boundary surface.

The following acids are suitable for the preparation of physiologically tolerable acid addition salts of the compounds of the formula I: hydrohalic acids such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, further phosphoric acid, nitric acid, sulfuric acid, monobasic and dibasic carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid and 1,5- naffalendisullOonic acid.

Acid addition salts of the compounds of formula I can be obtained in a simple manner according to conventional salt-forming methods, for example by dissolving the compound of formula I in a suitable inert solvent and adding an acid, for example hydrochloric acid, and isolated in a known manner. washing with an inert organic solvent.

The active substances useful according to the invention interfere with the metabolism of plants and can therefore be used as plant growth regulators.

For the type of action of the plant growth regulators, it has been known to date that the active ingredient can also have several different effects on the plant. The effects of these substances depend essentially on the time of application, depending on the developmental stage of the plant, as well as on the amount of active substance to be applied to or in the vicinity of the plant and on the method of application. In any case, plant growth regulators are intended to affect crop plants in some desirable manner.

Plant growth regulators can be used, for example, to suppress vegetative plant growth. Such growth suppression is of economic importance, inter alia, in grassland, since the suppression of grass growth may reduce, for example, the frequency of mowing in ornamental gardens, parks and sports facilities, at the edges of roads, at airports or in orchards. It is also important to suppress the growth of herbaceous and woody plants at roadside and close to oil pipelines and overhead lines, or quite generally where strong growth is undesirable.

It is also important to use plant growth regulators to suppress crop growth in grain, as this will reduce or eliminate the risk of plants lying down before harvest due to crop shortening. In addition, plant growth regulators can cause grain stalks to increase, which also counteracts lodging.

The use of growth regulators to shorten the stalks and strengthen the stalks allows the application of higher amounts of fertilizer to increase yields, without worrying about crop lodging.

Suppression of vegetative growth allows for many crops to be denser or planted, so that yields per unit area can be increased. The smaller plants thus grown also have the advantage that the culture is easier to cultivate and harvest.

Suppression of vegetative growth of plants can also lead to increased yields, as nutrients and assimilates are used more intensively to produce flowers and fruits than to grow vegetative parts of plants.

Stimulators of vegetative growth can also often be achieved with growth regulators. This is of great importance when vegetative parts of plants are germinating. However, stimulation of vegetative growth can also lead to stimulation of generational growth by producing more assimilates, so that for example more fruits can be formed or larger fruits can be produced.

Increased yields can also be achieved in many cases by interfering with the metabolism of the plants without observing any appreciable changes in vegetative growth.

Growth regulators can further influence the changes in the composition of plants, which in turn can achieve a better quality of harvested products. Thus, for example, it is possible to increase the sugar content of sugar beet, cane, pineapple and citrus fruits, or to increase the protein content of soybeans or cereals. Furthermore, it is possible, for example, to inhibit the degradation of the desired substances contained in plants, such as sugar in sugar beet or sugar cane, before or after harvesting by means of growth regulators. In addition, the product or effluent of secondary plant substances can be positively influenced. An example is the stimulation of latex effluent in rubber trees.

Parthenocarpic (seedless) fruits can also be produced by growth regulators. It is also possible to influence the sex of the flowers with these regulators. Pollen sterility can also be achieved, as is widely known in breeding and hybrid seed production.

Using growth regulators is. it is possible to control the formation of side shoots in plants. On the one hand, the development of lateral ones can be supported by violating apical dominance. This can be particularly desirable in the cultivation of ornamental plants, even in conjunction with growth suppression. On the other hand, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in the cultivation of tobacco or tobacco. when planting tomatoes.

The effect of the active ingredients on the plant press can be controlled so that the plants can be completely de-leafed at the desired point in time. Such defoliation is important for facilitating the mechanical harvesting of cotton, but also plays a major role in other cultures, for example. in vines, where it facilitates harvesting. Plant deflation can also be performed to reduce plant transpiration before transplanting.

Growth regulators can also be used to control the fall of fruit. On the one hand, it is possible to prevent premature decay of fruits, but on the other hand, the decay of fruits or even flowers in the sense of a "chemical thinning" can be encouraged to some extent to break the so-called "alternative". An alternative is the special behavior of some fruits, based on endogenous, very different yields from year to year. Growth regulators can also serve to tern to reduce the crop time needed for harvesting crops in crop plants, so that mechanical harvesting or manual harvesting is facilitated.

Further, growth regulators can be used to accelerate or slow down the ripening of harvested products before or after harvesting. This is particularly advantageous since it can be optimally adapted to market requirements. Furthermore, growth regulators can in many cases fold to improve the coloring of the fruit. In addition, growth regulators can achieve a concentration of fruit ripening within a certain period of time. This creates the prerequisites for, for example, tobacco, tomatoes or coffee plants to be able to carry out fully mechanical or manual harvesting in only one working stage.

The use of growth regulators can also affect seed or bud rest periods in plants, so that plants, such as pineapple or horticultural ornamental plants, germinate, sprout or bloom when they do not germinate, sprout or sprout under normal conditions. nekvetly.

Growth regulators can also achieve delayed bud growth, delayed seed germination, for example to prevent late frost damage in colder * climates,

Finally, plant growth regulators can be used to induce resistance to frost, drought or high salt content in the soil, allowing the plants to be grown in areas that they would not. were normally unsuitable for these plants.

The active compounds according to the invention have a strong microbicidal action and can be used for combating undesirable microorganisms for practical purposes. The active compounds are suitable as plant protection agents.

Fungicides are used in plant protection to combat fungi belonging to the classes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteruterycyces.

The good tolerability of the active substances in the concentrations necessary to combat plant diseases allows the treatment of above-ground parts of plants, seedlings and seeds, as well as the soil.

They can be effective as plant protection agents. The compounds according to the invention can be used with particular success in combating such compounds. fungi that cause true powdery mildew diseases.

So . can use to. combating fungi of the Erysiphe species, such as. for example, against powdery mildew (Erysiphe graminis) on barley and carcasses, and on combating fungi of the Podosphaera species, such as the causative agent of Podosphaera leucotrichaj and Sphaerotheca species, such as the Cucumber powdery mildew (Sphaerotheca) It should be noted that the active compounds useful according to the invention have a broad fungicidal effect in vitro, for example against Puccinia recondita.

In the respective application rates, the active compounds according to the invention also exhibit herbicidal properties.

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, small particles coated with polymeric substances and seed coatings, as well as compositions for the application of so-called ULV- procedure (Ultra — Law — Volume).

These. the compositions are prepared in a known manner, for example by mixing. active substances with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is possible. organic solvents, for example, can also be used as co-solvents. As. in principle liquid solvents are: aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or m-ethylene chloride, aliphatic hydrocarbons such as cyclohexane or raffinates, for example petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol esters, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Further, these compositions may contain colorants such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic colorants, such as alizarin dyes, azo dyes and metallic phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt salts. , molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90 prqc. active ingredient.

The active compounds according to the invention can be present in the formulations in admixture with other known active substances, such as fungicides, insecticides, acaricides and herbicides, as well as in mixtures with machinery fertilizers and other plant growth regulators.

The active compounds according to the invention can be applied as such, in the form of concentrates or further dilution forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. Is the application going in the usual way?

Further, the active compounds can be applied by the so-called ULV procedure (Ultra-Low-Volume) or the active agent or the active compound itself can be injected into the soil. Plant seeds may also be treated.

When using the compounds of the invention as plant growth regulators, their consumption can vary within wide limits. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active compound are used per hectare of soil surface.

When using the compounds according to the invention as growth regulators, the application is carried out for a preferred period of time, the definition of which is governed by climatic and vegetative conditions.

Also, when the active compounds according to the invention are used as fungicides, their consumption may, depending on the method of application, be varied within a wide range.

In the treatment of plant parts, the active compound concentration in the dosage forms is generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment of seed, generally 0.001 to 50 g of active compound, preferably 0.01 to 10 g of active compound, are to be used per kilogram of seed. In the treatment of the soil, the concentration of active ingredient at the place where the effect is to be achieved is from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight.

The following examples and biological activity tests illustrate the invention in more detail, but do not limit it in any way.

Examples illustrating the method of production of active ingredients:

Example 1

ch ₂

g (0.9 mol) of 80% sodium hydride is added portionwise at room temperature to a solution of 290 g (0.86 mol) of 2- (4-chloro-2-methylphenoxymethyl) -3,3-dimethyl-1- ( 1,2,4-triazol-1-yl) -2-butanol in 1600 ml absolute dioxane. The reaction mixture was further stirred at room temperature for 4 hours, then 141.9 g (1 mol) of iodomethane was added dropwise, and the reaction mixture was stirred at 40 ° C for 12 hours. (33 mol) of 80% sodium hydride After stirring at room temperature for 3 hours, 57 g (0.4 mol) of iodomethane are added to the reaction mixture and the reaction mixture is further stirred at room temperature for 72 hours. The oily residue is taken up in dichloromethane, washed twice with water, dried over sodium sulphate and concentrated and 1,5-naphthalenedisulphonic acid is added to the residue in acetone, the precipitated salt is filtered off, washed with acetone, suspended in dichloromethane and saturated solution is added. The organic phase was separated, washed and concentrated to give 155 g (54% of theory) of 2- (4-chloro-2-methyl-phenoxymethyl) -3,3-dimethyl-2-methoxy-1- (1). 2,4-triazol-1-yl) butane in the form of a light yellow oil having a refractive index n _D ^{2 ()} = 1.5390.

The following compounds of formula I are obtained in an analogous manner and in accordance with the process of the invention

OR ² in -CH ₂ -cr ¹

Zm ^z CH ₉ . - I ² example number Zm у / Nx ^J В Rl R ² (and) melting point

(° C) optionally ²⁰

2 4-C1 O C (CH3) ₃ СНз 198—203 (х НС1) 3 2,4-Cb O С (СН ₃ ) з СНз 1,5382 4 4-C1 CH ₂ C (CH ₃ j ₃ СНз 1,5354 5 4-F CH ₂ C (CH3) ₃ СН ₃ 1.5212

Examples illustrating biological activity:

In the following examples, which illustrate the application possibilities of the compositions according to the invention, the following compounds A to E are used as comparative compounds:

(A) (B)

OH

/ = N

CH ₂ -NJ

сн ₂

(E)

Example A

Test for powdery mildew Sphaeroteca fuligínea (cucumber) / protective effect

Solvent:

0.7 parts by weight of acetone

Emulsifier:

0.3 part by weight of alkylaryl polyglycol ether

To obtain a suitable active agent, 1 part by weight of active ingredient is mixed with the indicated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

In order to test the protective effect, young plants are sprayed with the active agent up to the wetting stage. After the spray layer has dried, the plants are dusted with conidia of Sphaeroteca fuligínea.

The plants are then placed in a greenhouse at 23-24 ° C and a relative air humidity of about 75%.

days after inoculation, evaluation of the experiment is performed.

In this test, for example, the compounds according to the following examples show a significantly better effect compared to the prior art: 1, 3 and 4.

The results are shown in Table A below:

Table A

Test for powdery mildew of Sphaerotheca fuligínea (cucumbers) - protective effect of active substance infestation in% at active substance concentration

0.0005%.

(known substance)

Cl

CH 3 ^OCH 3

Cl - $ OCH ^2_ C ^{С; С} ^ ^н ^ 2)) з

CHo

I «5 *

N- (1)

237'3 3 5

(3)

Cl

......... OCH ₃ —CH2CH2-C - (2) for ₂ .

(4)

Example B

Test for apple powdery mildew (Podo-sphaera leucotricha) (apple / protective effect

Solvent ·:

4.7 parts by weight of aacton

0.3 part by weight of alkylaryl polyglycol ether

To obtain a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

In order to test the protective effect, young plants are sprayed with the active ingredient up to. dew condensation. After the spray layer has dried, the plants are dusted with conidia of the powdery mildew of the apple tree (Podosphaera leucotricha).

The plants are then placed in a greenhouse at 23 ° C and a relative air humidity of about 70 ^L %.

days after inoculation, evaluation of the experiment is performed.

In this test, they show a clear superiority in activity compared to the prior art, for example the compounds according to the following examples: 1, 2, 3 and

4.

The results of this test are shown in Table B below:

Table В

Test for apple powdery mildew (Podosphaera leucotricha) (apple tree) - protective effect of the active substance attack in ° / o at the concentration of the active substance

0.0005%

(known)

Cl / HCl

Г2)

Cl

^Cl 2 Z 2 ^-CH 2 ^CH 2 -? -C ( ^CH ₃ ) ₃

CH ₉ i

N --- u (3)

Example С

Powdery mildew test (Erysiphe graminis f.

properties Sp. (barley) / protective effect

Solvent:

100 parts by weight of dimethylformamide

0.25 parts by weight of alkylaryl polyglycol ether

To obtain a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of emulsifier and solvent, and the concentrate obtained is diluted with water to the desired concentration.

To test the protective effect, young plants are sprayed with the active agent. After the spray layer has dried, the plants are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are then placed in a greenhouse at a temperature of about 20 ^° C and a relative air humidity of about 80 to favor the development of powdery mildew populations.

days after inoculation, evaluation of the experiment is performed.

In this test, for example, the compounds according to the following examples show a clear superiority in activity compared to the prior art: 2, 1, 3 and 4.

The results of this test are shown in Table C below:

Table C

Test for powdery mildew (Erysiphe graminis f.sp. hordei) (barley) - protective effect active substance concentration of active substance in spray suspension (% by weight) disease attack in% of untreated control

OH

0,025 100

0.025 0.0 ch ₂

0,025

0.0

(1) active substance concentration of active substance in spray suspension (% by weight) disease attack in% of untreated control (3)

Cl

0,025

0.0

Cl

OCHo

I ³ - CH ² CH 2 -C 8 (s) ₃

0,025

0.0

CH2.

(4)

Example D

Wheat rust test (Puccinia recondita) (wheat) - protective effect

Solvent:

100 parts by weight of dimethylformamide

0.25 parts by weight of alkylaryl polyglycol ether

To obtain a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount, solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective action, young plants are inoculated with a suspension of wheat spores (Puccinia recondita) in 0.1% aqueous agar solution. After drying, the plants are sprayed with the active ingredient until dripping. The plants are then kept for 24 hours in an incubation chamber at 20 degrees Celsius and 100% relative humidity.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and a relative air humidity of about 80 ° C to favor the development of rust stacks.

days after ¹ inoculation, evaluation of the experiment is performed.

In this test, for example, the following compounds of the Examples exhibit a clear superiority in action over the known prior art: 2, 1, 3 and 4,

The results of this test are shown in Table D below:

Test for wheat rust (Puccinia recondita) (wheat) - protective effect of concentration of the active substance in the spray suspension (in '% by weight') infested with disease in% of untreated control

Table D active substance

0.01

0.01

58.8

0.0

(1) (3)

OCHo

0.01

0.01

0.0

0.0

0.01

0.0

CH2.

(4)

Example E

Powdery mildew test (Erysiphe graminis f. Sp. Hordei) (barley / seed treatment

The application of the active ingredients is carried out in the form of a dry stain. The mordant is prepared by mixing the respective active ingredient with stone flour to form a finely divided mixture which ensures uniform distribution on the seed surface.

Pickling is carried out by shaking the seed with the dressing for ¹ minute in a closed glass bottle.

The barley is then sown in 3 x x 12 grains 2 cm deep into the standard mine. 7 days after sowing, when young plants have developed their first leaf, the plants are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20 ° C and a relative air humidity of about 80% to favor the development of powdery mildew piles.

days after inoculation, evaluation of the experiment is performed.

In this test, for example, the compounds according to the following Examples exhibit a clear superiority in activity compared to the state of the art: 2, 1, 3 and 4.

The results of this test are shown in Table E below:

Table E

Powdery mildew test (Erysiphe graminis f.sp. hordei) (barley)

.100 100

1000

0.0

1000

0.0 (1)

1000

0.0 (4)

Example F

Influence of sugar beet growth

Solvent:

parts by weight of dimethylformamide

part by weight of polyethylene sorbitan monolaurate

In order to produce a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate obtained is made up to the desired concentration with water.

Sugar plants are grown in the greenhouse until the cotyledons are completely formed. At this stage, the plants are sprayed until the active ingredient is treated. After 14 days, the plant growth is measured and the growth influence in percent growth of the control plants is calculated. In doing so, 0 · ·% of the growth effect means growth corresponding to that of the control plants. Negative values indicate growth retardation, positive values indicate growth stimulation compared to control plants.

In this test, the active compounds according to the embodiments 2, 1, 3 and 4 show a stronger growth effect than compounds B, D and E, which are known in the art.

The results of this test are shown in the following table · F:

23733S growth influence in%

Table F

Effect on sugar beet growth active ingredient concentration in '% (B)

OH

0.05 +5 (D) (known)

0.05 +5

0.05 (E) (known)

OCH »

AND

СН 2-С-С (СНз) ₃

СН2 x HCi

0.05 —85 *

0.05 __70 *> **)

ОСНз

I ³ ₂ -СН СН -С ₂ - ^^ (CH3) ₃

0.05 —80 ^й * ·) (4]

CH?

AND

Μ • ιΜ * 'dark green leaf color **' thick leaves

Example G

Cotton growth inhibition

Solvent:

parts by weight of dimethylformamide

part by weight of polyoxyethylene sorbitan monolaurate

In order to obtain a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier and the mixture obtained is made up. water. to the desired concentration.

Cotton plants are grown in the greenhouse until the fifth assimilation leaf is fully unfolded. At this stage, the plants are sprayed with the active ingredients until wet. After three weeks, the plant growth is measured and the growth retardation is calculated as a percentage of the control plant growth. 100% inhibition of growth means a rest state (plants do not grow) and 0% inhibition of growth corresponds to that of control plants.

In this test, the active compounds of Examples 2, 3 and 1 show better growth retardation than the compounds B, D and E known in the art.

Results. of this test are shown in Table G below:

Table G

Cotton growth inhibition active substance concentration in% Cotton growth inhibition in%

OH

(D) (known)

0.05 0

0.05 10

(1) з> dark green · leaf color

0.05

55 · »

0.05

35 *>

Example H

Soy growth inhibition

Solvent ·:

parts by weight of dimethylformamide

part by weight of polyoxyythylene sorbitan monolaurate

To produce a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is made up to the desired concentration with water.

Soybean plants are grown in the greenhouse until the first assimilation leaf is completely formed. At this stage, the plants are sprayed with the active ingredients up to the wetting stage.

After 3 weeks, all plants were measured for growth and the inhibition of growth was calculated as a percentage of control growth. 100% inhibition of growth means a rest state (plants no longer grow) and 0% inhibition of growth represents growth corresponding to that of control plants.

The active compounds according to the invention from the examples

Tables H of Embodiments 2, 1, 3 and 4 show stronger growth retardation in this test than compounds A, V, and D known in the art.

The results of this test are shown in Table H below:

Soybean growth inhibition Active substance concentration in% Soybean growth inhibition%

OH

(known) (known)

HCl

0.05

0.05

0.05

0.05

95 * »(2) active substance concentration% growth inhibition%

0.05

95 *>

(1)

0.05

85 ^#)

OCH ₃

CH ₂ CH ₂ -C -C (CH ₃ ) ₃

CHp

I • li-J (4) ^#) dark green leaf color

0.05

65 * ¹

Claims (3)

OBJECT OF THE INVENTION A fungicidal and plant growth regulating agent, characterized in that it contains at least one substituted 1-hydroxyixalkylazole ether derivative of the general formula I as an active ingredient. R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, Z is halogen or a (C 1 -C 4) alkyl group, and m is 1 or 2, or an acid addition salt thereof. 2. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R ¹ is tertiary butyl, isopropyl or methyl, Z represents fluoro, chloro, bromo, methyl or tert-butyl, R ² represents methyl, ethyl, n-propyl, isopropyl (I) wherein B represents oxygen or a group N ₂ , a polyl group, an n-butyl group, an isobutyl group, and В and m have the meanings given in point 1. 3. A process for the preparation of the active ingredient of the formula I as well as the corresponding acid addition salts, characterized in that the alkoxides of the 1-hydroxyalkylazoles of the formula II are reacted. OM in which B, R ¹ , Z and m are as defined above and M is an alkali metal, a quaternary ammonium group or a phosphonium group, with a halide of formula III R ² -Hal (III) in which R ² has the abovementioned meaning and Hal is halogen, in the presence of a diluent at a temperature between 0 and 120 ° C, and optionally an acid is added to the compound of formula (I) thus obtained.